Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/87—Polyurethanes
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q3/00—Manicure or pedicure preparations
  • A61Q3/02—Nail coatings
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
  • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
  • C08G18/0828—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing sulfonate groups or groups forming them
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
  • C08G18/3857—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur having nitrogen in addition to sulfur
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
  • C08G18/3889—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/54—Polymers characterized by specific structures/properties
  • A61K2800/542—Polymers characterized by specific structures/properties characterized by the charge
  • A61K2800/5424—Polymers characterized by specific structures/properties characterized by the charge anionic

Definitions

• the present invention relates to novel anionic polyurethanes with elastic property and to their use in cosmetic compositions.
• T g glass transition temperatures
• the subject of the present invention is consequently anionic polyurethanes with elastic property, essentially consisting
• nonionic units derived from at least one nonionic monomer or polymer compound having at least two reactive functions with labile hydrogen
• At least one type of units (a1) and (a2) is derived from a polymer having a glass transition temperature (Tg), measured by differential scanning calorimetry, less than 10° C. and that these sequences with Tg less than 10° C. represent from 20% to 90% of the total weight of the polyurethane.
• Tg glass transition temperature
• the subject of the invention is also the use of the above anionic polyurethanes with elastic property in cosmetic compositions in order to improve the viscoelastic properties of the cosmetic deposits and films obtained from these compositions.
• the subject of the invention is also cosmetic compositions containing the above anionic polyurethanes with elastic properties.
• the above anionic polyurethanes may also be used to improve the staying power of makeup compositions for the skin, the lips and the superficial body growths.
• the deposits obtained follow the deformations of the keratinous substrates and do not pull the skin.
• the presence of the anionic fillers confers on the polyurethanes of the present invention a fairly hydrophilic nature independent of the pH of the medium containing them.
• the anionic polyurethanes of the present invention are consequently soluble, or at least dispersible, in polar solvents and in particular in water and lower alcohols, which greatly facilitates their formulation in cosmetic compositions.
• the anionic polyurethanes with elastic property of the present invention essentially consist of three types of unit which are
• sulfonic acid function and “phosphonic acid function” denote not only the protonated acid form of these functions but also the forms partially or completely neutralized with a base, that is to say the sulfonate (—SO 3 ⁇ ), phosphonate (—PO 3 H ⁇ ) and diphosphonate (PO 3 ⁇ 2 ) groups.
• reactive functions with labile hydrogen is understood to mean functions which are capable, after departure of a hydrogen atom, of forming covalent bonds with the isocyanate functions of the compounds forming the units (b). There may be mentioned by way of example of such functions hydroxyl, primary amine (—NH 2 ) or secondary amine (—NHR) groups, or alternatively thiol (—SH) groups.
• the compounds with sulfonic and/or phosphonic acid function forming the units (a1) carry more than two functions with labile hydrogen, the polyurethanes obtained have a branched, optionally even crosslinked, structure.
• the compounds with sulfonic and/or phosphonic acid function forming the anionic units (a1) have only two reactive functions with labile hydrogen and the polyurethanes obtained by polycondensation consequently have an essentially linear structure.
• the compounds with sulfonic and/or phosphonic acid function forming the anionic units (a1) are preferably chosen from the compounds corresponding to one of the following formulae:
• Acid represents a sulfonic acid or a phosphonic acid group, in protonated or salified form
• each R a independently represents a direct bond or a linear or branched C 1-6 alkylene group, a C 3-6 cyclo-alkylene group or an arylene group, it being possible for all to be substituted with one or more halogen atoms and to contain one or more heteroatoms chosen from O, P and S,
• R b represents a hydrogen atom or an alkyl group which may contain one or more heteroatoms chosen from O, P and S,
• Y represents a saturated, unsaturated or aromatic, cyclic C 5-10 group optionally containing one or more heteroatoms chosen from O, P and S,
• each X independently represents an oxygen or a sulfur atom or an NH or NR c group, where R c represents a C 1-6 alkyl group.
• the reactive functions with labile hydrogen are amine functions, that is to say in the formulae (I) to (IV) above X ⁇ NH or NR c , giving polymers of the polyurea type.
• the polyureas indeed form films which are distinguishable by an excellent cohesion which improves the retention of the hairstyle or the abrasion resistance of the nail varnishes containing these polyureas.
• the compounds with sulfonic and/or phosphonic acid function forming the anionic units (a1) of the polyurethanes of the present invention may also be polymers.
• anionic polymers with sulfonic and/or phosphonic acid function may be obtained, in one step, by free-radical, anionic or cationic copolymerization, and in particular by ring opening, or by polycondensation of nonionic monomers and of anionic monomers carrying sulfonic acid or phosphonic acid units.
• anionic monomers which can be used for the free-radical polymerization of sodium styrenesulfonate.
• the polymers may also be obtained in two steps, that is to say by polymerization or polycondensation of nonionic monomers, followed by the grafting of units with sulfonic or phosphonic acid function.
• the nonionic monomers which can be used are for example vinyl monomers, ethylene oxide or propylene oxide.
• the polymers obtained by polycondensation may be polyesters, polyamides or polyurethanes.
• the sulfonic acid or phosphonic acid functional groups may also be introduced by initiators carrying these functions.
• the groups with labile hydrogen may be introduced by monomers, initiators or chain terminating agents carrying such groups.
• the weight-average molecular mass of these polymers with sulfonic and/or phosphonic acid functions is preferably between 200 and 10 000, and more preferably between 400 and 5000.
• n is between 2 and 100.
• the second type of units forming the polyurethanes of the present invention are nonionic monomer or polymer units, called units (a2), carrying at their ends reactive functions with labile hydrogen.
• nonionic units (a2) While the presence of the anionic units (a1) and of the units (b) derived from diisocyanates is obligatory in the polyurethanes of the present invention, that of the nonionic units (a2) is optional. These nonionic units may be derived from monomers or from polymers.
• the nonionic polymers capable of forming the units (a2) are chosen for example from polyethers, polyesters, polysiloxanes, copolymers of ethylene and butylene, polycarbonates, polyalkyl (meth)acrylates and fluorinated polymers.
• the polyethers are most particularly preferred, and among them poly(tetramethylene oxide).
• the weight-average molar mass of these nonionic polymers is preferably between 400 and 10 000 and more particularly between 400 and 5000.
• the elastic property of the polyurethanes of the present invention is linked to the simultaneous presence, in the polymer, of a certain fraction of polymer sequences having a glass transition temperature less than 10° C., and a certain fraction of units forming sequences which have a glass transition temperature greater than room temperature.
• sequences having a glass transition temperature less than 10° C. are formed by the anionic polymers and/or the nonionic polymers described above.
• the viscoelastic properties of the anionic polyurethanes of the present invention are particularly advantageous when the units (a1) or (a2) are derived from polymers having a glass transition temperature less than 0° C. and better still less than ⁇ 10° C.
• sequences with Tg greater than 20° C. also called “rigid” sequences, exist, at room temperature, in the glassy state and thus form physical crosslinking nodes of the three-dimensional polymer network.
• the elasticity of the polyurethanes of the present invention is satisfactory when the fraction of anionic or nonionic polymer units having a glass transition temperature less than 10° C. represents from 20 to 90%, preferably from 20 to 80%, and in particular from 20 to 70% of the total weight of the polyurethanes of the present invention.
• the diisocyanates forming the units (b) include aliphatic, alicyclic or aromatic diisocyanates.
• Preferred diisocyanates are chosen from methylene-diphenyl diisocyanate, methylenecyclohexane diisocyanate, isophorone diisocyanate, toluene diisocyanate, naphthalene diisocyanate, butane diisocyanate and hexyl diisocyanate. These diisocyanates may of course be used alone or in the form of a mixture of two or more diisocyanates.
• the elastic property of the anionic polyurethanes of the present invention is due to the fact that these polymers have at least two different glass transition temperatures (Tg), at least one of these Tg being less than 10° C. and at least another being greater than or equal to 20° C.
• Tg glass transition temperatures
• the physical parameter characterizing the viscoelastic properties of the above anionic polyurethanes is their tensile recovery. This recovery is determined by a tensile creep test consisting in rapidly stretching a test piece to a predetermined degree of elongation, and then in releasing the stress and measuring the length of the test piece.
• test piece a polyurethane film having a thickness of 500 ⁇ 50 ⁇ m, cut into 80 mm ⁇ 15 mm strips.
• This copolymer film is obtained by drying, at a temperature of 22 ⁇ 2° C. and at a relative humidity of 50 ⁇ 5%, a solution or dispersion at 3% by weight of said polyurethane in water and/or ethanol.
• Each strip is fixed between two jaws 50 ⁇ 1 mm apart, and is stretched at a speed of 20 mm/minute (under the temperature and relative humidity conditions above) up to an elongation of 50% ( ⁇ max ), that is to say up to 1.5 times its initial length.
• the stress is then released by imposing a speed of return equal to the tensile speed, that is 20 mm/minute, and the elongation of the test piece (expressed as a percentage relative to the initial length) immediately after returning to zero loading ( ⁇ i ) is measured.
• R i (%) (( ⁇ max ⁇ i )/ ⁇ max ) ⁇ 100
• the anionic polyurethanes with elastic property of the present invention preferably have an instantaneous recovery (R i ), measured under the conditions indicated above, between 5% and 100%, in particular between 20% and 100% and ideally between 35 and 100%.
• R i instantaneous recovery
• Tg glass transition temperatures of the polymers forming the units (a1) or (a2) and of the anionic polyurethanes of the present invention are measured by differential scanning calorimetry (DSC) according to the ASTM D3418-97 standard.
• the instantaneous recovery, and consequently the viscoelastic properties of the polyurethanes of the present invention depends on the proportions of the different units (a1), (a2) and (b) in the polymer.
• fraction of units (a1) should be sufficient to confer on the polymers their negative charge responsible for their good capacity to dissolve or to be dispersed in polar solvents such as water and alcohols.
• the anionic polyurethanes of the present invention preferably have an anionic charge level between 0.1 and 15 milliequivalents per gram (meq/g), more preferably between 0.1 and 10 meq/g, and most particularly between 0.1 and 5 meq/g.
• the units (a1) represent in particular from 1 to 90% and preferably from 5 to 60% by weight, and the units (a2) advantageously represent from 0 to 90% and preferably from 40 to 70% by weight of the total polymer.
• the units (b) are present in an essentially stoichiometric quantity relative to the sum of the units (a1) and (a2). Indeed, the production of polyurethanes having high molar masses assumes a number of isocyanate functions which is practically identical to the number of functions with labile hydrogen. Persons skilled in the art will know how to choose a possible molar excess of either type of function in order to adjust the molar mass to the desired value.
• the anionic polyurethanes with elastic property may be incorporated into numerous cosmetic compositions of which they improve the cosmetic properties.
• the quantity of polyurethane present in the various compositions of course depends on the type of composition and the desired properties and may vary within a very broad range, generally between 0.5 and 90% by weight, preferably between 1 and 50% by weight, relative to the final cosmetic composition.
• anionic polyurethanes with elastic property When incorporated into hair lacquers, their concentration is generally between 0.5 and 15% by weight. In nail varnishes, they generally represent from 0.5 to 40% by weight of the composition, and makeup compositions for the skin, the lips and superficial both growths generally contain 0.5 to 20% by weight of the polyurethanes of the present invention.
• a quantity of THF such that the concentration of diol type monomers is equal to 75% by weight.
• the reaction mixture is allowed to cool to room temperature, and then diluted with acetone to a polymer concentration of about 40% by weight.
• the organic phase is then removed by distillation under vacuum at a temperature of 40° C.
• Polyurethane films are prepared from dispersions at. 3% by weight of the polyurethane of Example 1 in a water/ethanol (1/2) mixture.
• the instantaneous recovery (expressed as %) is measured under the following conditions:
• thickness of the film 500+50 ⁇ m
• drying conditions 22 ⁇ 2° C., relative humidity of 50 ⁇ 5%,
• stretching speed return speed: 20 mm/minute.
• R i (%) (( ⁇ max ⁇ i )/ ⁇ max ) ⁇ 100

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• Health & Medical Sciences (AREA)
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• Animal Behavior & Ethology (AREA)
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• Birds (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
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• Polyurethanes Or Polyureas (AREA)
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Citations (12)

• 2001
  • 2001-03-05 FR FR0102947A patent/FR2821621B1/fr not_active Expired - Fee Related
• 2002
  • 2002-02-27 EP EP02708418A patent/EP1373346A1/fr not_active Withdrawn
  • 2002-02-27 US US10/469,785 patent/US20040197293A1/en not_active Abandoned
  • 2002-02-27 WO PCT/FR2002/000703 patent/WO2002070577A1/fr not_active Ceased
  • 2002-02-27 JP JP2002570612A patent/JP2004529228A/ja active Pending

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